CN1970582A - Poly(N- ethenyl-N'-alkyl- imidazole) ion liquid structural material and its preparation method - Google Patents
Poly(N- ethenyl-N'-alkyl- imidazole) ion liquid structural material and its preparation method Download PDFInfo
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- CN1970582A CN1970582A CN200610098208.7A CN200610098208A CN1970582A CN 1970582 A CN1970582 A CN 1970582A CN 200610098208 A CN200610098208 A CN 200610098208A CN 1970582 A CN1970582 A CN 1970582A
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- ionic liquid
- vinyl
- imidazoles
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- 239000000463 material Substances 0.000 title claims abstract description 33
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000007788 liquid Substances 0.000 title description 7
- 239000002608 ionic liquid Substances 0.000 claims abstract description 52
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims description 23
- 229920002554 vinyl polymer Polymers 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 230000026030 halogenation Effects 0.000 claims description 4
- 238000005658 halogenation reaction Methods 0.000 claims description 4
- 239000003495 polar organic solvent Substances 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001350 alkyl halides Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000015598 salt intake Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 16
- 239000000376 reactant Substances 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 description 19
- -1 transistor Substances 0.000 description 16
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- VWFFMMQJLCFPJE-UHFFFAOYSA-N fluorophosphonic acid 1H-imidazole Chemical compound P(=O)(O)(O)F.N1C=NC=C1 VWFFMMQJLCFPJE-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000031709 bromination Effects 0.000 description 6
- 238000005893 bromination reaction Methods 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical class CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical class CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010205 computational analysis Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a poly-N-vinyl-N'-alkyl-imidazole ionic liquid structure material, which possesses general structure on the right, wherein R is C2-C16 alkyl; X is negative ion; n and m is chain segment number with and without ionized group; the scale of the rate of n and n+m is 0.1:1-1:1, which is adjusted by the molar rate of reactant; the polymer molecular quantity scale is (0.1-100)*104g/mol.
Description
Technical field
The present invention relates to the product of polyvinyl imidazol and halohydrocarbons reaction---poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material and preparation method thereof.
Background technology
As a kind of environmentally friendly novel Green Chemistry material, ion liquid research has obtained paying close attention to widely.Because the electrochemical window and non-volatile, the advantage such as do not burn of thermostability preferably, higher ionic conductivity, broad are arranged, ionic liquid has a wide range of applications at aspects such as the galvanic deposit of secondary cell, photocell, double layer capacitor, transistor, metal and membrane sepn.But ionic liquid has runny shortcoming as a kind of liquid, makes troubles for the application of some occasion.Generally speaking, the specific conductivity of polymkeric substance is lower, but has advantages such as easily making different shape, easy processing, easy film forming.Therefore, ionic liquid is combined with polymer phase, the synthetic high molecular polymer that contains the ionic liquid structure will have the advantage of ion liquid high conductivity and polymkeric substance excellent in mechanical properties concurrently.
Ion liquid synthesizing mainly is to synthesize the halogenide of quaternary ammonium by tertiary amines and halohydrocarbon, and then as required, further the halogen negative ion is exchanged for desired negative ion.At present, research is maximum, and the tertiary amines material that is most widely used is the compound that contains the imidazole ring structure.For obtaining conductive polymers, a few studies person has carried out introducing the research of ionic liquid structure in polymer both at home and abroad, at present report mainly contains 4 kinds of method [Zhang Zhen's beautiful jades, Wang Rongmin, Wang Yunpu, Xia Chungu, the polymer circular, 2004, (2), 63-69]: (1) puts into the ionic liquid initiated polymerization with monomer; (2) introduce the ionic liquid structure in the monomer, the re-initiation monomer polymerization forms conducting polymer, and some inorganic salt that can mix therein are to improve specific conductivity; (3) absorb ionic liquid with polymeric film; (4) ionic liquid and high molecular blended complex.More than in 4 kinds of methods the 2nd kind, promptly obtain the polymerization of ionic liquid topology convergence monomer re-initiation earlier, the polymkeric substance that provides is a homogeneous, promptly the chemical constitution of each repeating segment of polymkeric substance, ionic liquid structure are all consistent, make polymer architecture lack adjustability.People such as M.Hirao (Electrochimica Acta, 45,1291,2000) and people (Journal of Polymer Science:Part A:Polymer Chemistry such as R.Marcilla, 42,208,2004) all reported the imidazoles synthesis method for high molecular polymer that contains the ionic liquid structure, the method that they take is exactly above-mentioned second method.Though people's such as M.Watanabe research (Electrochimica Acta, 40,2285,1995) taked the first monomer polymerization of using, introduce the synthetic route of ionic liquid structure again, but its research is the pyridines ion liquid polymer, and this research does not relate to yet and contains ionic liquid structure segmental molar fraction in the controlling polymers.
Summary of the invention
The objective of the invention is in polymkeric substance to introduce the ionic liquid structure, provide a kind of have high conductance by polyvinyl imidazol and halogenated alkane reaction synthetic polymer ions salt, and as required, the halogen negative ion can be exchanged for desired negative ion.
Another object of the present invention provides a kind of preparation method by polyvinyl imidazol and halogenated alkane reaction synthetic polymer ions salt of the present invention.
Technical scheme of the present invention is as follows:
A kind of poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material, it has following general formula:
Wherein R is C
2-C
16Alkyl, X-represents negative ion, the chain hop count that n, m represent to contain the chain hop count of ionogen respectively and do not contain ionogen, the ratio of n and m is regulated by the mol ratio of reactant adding, n: scope (n+m) is 0.1: 1～1: 1; Polymericular weight Mn scope is (0.1-100) * 10
4G/mol.
Above-mentioned poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material, described R is C
2-C
16Alkyl be meant straight or branched alkyl, for example ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 16 alkyl or isobutyl-etc. with 2-16 carbon atom.Negative ion is meant Cl
-, Br
-, I
-Deng halogen anion or BF
4 -, PF
6 -, CF
3SO
3 -, (CF
3SO
2)
2N
-, (CF
3CF
2SO
2)
2N
-, CF
3COO
-In negative ion.Poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material preferred of the present invention, wherein R is a straight chained alkyl.Most preferred poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material of the present invention, wherein R is a normal-butyl, X
-Be BF
4 -Or PF
6 -
The method of above-mentioned poly-(N-vinyl-N '-alkyl-imidazoles) the ionic liquid structured material of a kind of preparation, it may further comprise the steps:
The preparation of poly-(N-vinyl imidazole):
With the N-vinyl imidazole is monomer, and AIBN (Diisopropyl azodicarboxylate) is an initiator, and (the Mn scope is 0.1-100 * 10 to adopt free radical solution polymerization to obtain certain molecular weight
4G/mol) poly-(N-vinyl imidazole), synthetic method is according to common textbook [the safe chief editor of Golden Customs, the theory of polymer chemistry and application progress, Sinopec press, March nineteen ninety-five, first version] [A.Chapiro that describe or bibliographical information, et.al.Eur.Polym.J., 1988,24,69] method is carried out.
The preparation of poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material:
Step 1, polyvinyl imidazol is dissolved in the polar organic solvent;
Step 2, in the solution of step 2 gained, add the C of certain mole proportioning according to the monomeric mole number of institute's dissolved polyvinyl
2-C
16Halogenated alkane;
Step 3, with vlil 3-72 hour of step 3 gained, the preferred reaction times is 5-10 hour;
Step 4, stopped reaction steam reaction solvent, again product are dried to constant weight, obtain poly-(N-vinyl-N '-alkyl-imidazoles) the ionic liquid structured material of halogenation.
The preparation method of above-mentioned poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material, the polar organic solvent described in the step 1 is bigger alcohols of polarity or nitrile, as ethanol, Virahol, or acetonitrile etc.
The preparation method of above-mentioned poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material, the mole number of the haloalkane that step 2 added by step 1 dissolved polyvinyl imidazol segment mole number 0.1-2 doubly, to obtain having poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material of different charge numbers, the mole number of preferred haloalkane is 0.2～1.2 times.
Poly-(N-vinyl-N '-alkyl-imidazoles) the ionic liquid structured material of the above-mentioned halogenation that obtains can be further carries out negative ion exchange with ammonium salt or sylvite or sodium salt etc. with required negative ion according to the method for chemical field routine in solvent, make the salt of poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material of required target negative ion.
The preparation method of above-mentioned poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material, the solvent that the negative ion clearing house is used can be water, ethanol or water and ethanol mixed solvent, the salt consumption of target negative ion is 1.0～2.0 times of poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material ionization segment mole number, the permutoid reaction time is 0.5-72 hour, the permutoid reaction temperature is 0～50 ℃, and preferred above range of parameter values is respectively 1.0-1.2 times, 5-10 hour, 20-40 ℃.
The present invention has introduced the ionic liquid structure in polymkeric substance, and obtains the polymer ions liquid of required electrically charged number by the add-on that is controlled at halogenated alkane reactant in the reaction process.Advantages such as the Heat stability is good that the existing ionic liquid of polymkeric substance of the present invention is had, ionic conductivity height, electrochemical window are wide, the good mechanical property that also high molecular polymer is arranged and had, easy advantage such as processing.Simultaneously, polymer ions salt synthetic method of the present invention is simple, and building-up process is easy to operate and control.Polymer ions salt of the present invention is with a wide range of applications at aspects such as battery, electrical condenser, transistor, galvanic deposit.
Embodiment
Embodiment 1
In 23.5 gram vinyl imidazole monomer (counting 0.25 mole) the 150ml three-necked flasks that have reflux condensing tube and filling tube of packing into, add benzene, make solution become 80ml, stir the degassing, inflated with nitrogen protection.After being dissolved in 0.1g azobis isobutyronitrile (AIBN) in the 5ml benzene, place filling tube.Heating flask to 60 ℃ joined AIBN solution the flask from filling tube in one minute, and polyreaction begins.After the polyreaction 3 hours, boil off solvent, under 80 ℃ in vacuum drying oven vacuum-drying 24 hours to constant weight, obtain polyvinyl imidazol.Adopting Weighing method to carry out computational analysis, is 82.0% to add vinyl imidazole monomer reaction conversion ratio.
Embodiment 2
4.7 gram (in 0.05 mole of vinyl imidazole monomer) polyvinyl imidazols are packed into and had in the three-necked flask of reflux condensing tube; add 100 gram dehydrated alcohols and make its dissolving; add again 8.2 the gram (0.06 mole) bromination of n-butane (with vinyl imidazole monomer meter mole ratio be 1.2: 1); under whipped state, be warming up to alcohol reflux by thermostatic bath; reaction continues 24 hours, keeps faint nitrogen gas stream as protection gas in entire reaction course.Steam the used alcohol solvent of reaction, reaction product with vacuum drying oven 80 ℃ of following vacuum-dryings 24 hours to constant weight, obtain bromination normal-butyl polyvinyl imidazol, be 85.0% in vinyl imidazole monomer reaction bonded rate.
Embodiment 3
Repeat embodiment 2, add 10.9 gram (0.1 mole) monobromethanes (with vinyl imidazole monomer meter mole ratio be 2: 1) to replace bromination of n-butane, be 89.3% in vinyl imidazole monomer reaction bonded rate.
Embodiment 4
Repeat embodiment 2, add 1.5 gram (0.005 mole) bromo n-hexadecanes (with vinyl imidazole monomer meter mole ratio be 0.1: 1) to replace bromination of n-butane, be 91.3% in vinyl imidazole monomer reaction bonded rate.
Embodiment 5
Repeat embodiment 2, resulting product is all put into Erlenmeyer flask, add 50 ml deionized water make its dissolving after, under the stirring at room state, add 9.2 gram (0.05 mole) hexafluorophosphoric acid potassium, react 3 hours after-filtration, the solid that obtains obtains normal-butyl polyvinyl imidazol fluorophosphate (ionic liquid chain hop count is 85.0%), yield 89.3% through the oven dry of washing back.Results of elemental analyses: C:37.94%; H:5.14%; N:10.54% (calculated value: C:37.73%; H:5.24%; N:10.62%).Its second-order transition temperature is 158 ℃, INFRARED SPECTRUM: wave number (cm
-1): 3644.6,3392.0,2960.3,2876.6,1647.6,1572.8,1554.3,1232.5,1163.8,1113.3,1087.0,834.4,661.9,556.8.
Embodiment 6
Repeat embodiment 2, difference be to add 1.4 gram (0.01 mole) bromination of n-butane (with vinyl imidazole monomer meter mole ratio be 0.2: 1).Resulting product is 19.7% in vinyl imidazole monomer reaction bonded rate.
Embodiment 7
Repeat embodiment 2, difference be to add 3.4 gram (0.025 mole) bromination of n-butane (with vinyl imidazole monomer meter mole ratio be 0.5: 1).Resulting product is 38.5% in vinyl imidazole monomer reaction bonded rate.
Embodiment 8
Repeat embodiment 6, resulting product is all put into Erlenmeyer flask, add 50 ml deionized water make its dissolving after, under whipped state, add 1.8 gram (0.01 mole) hexafluorophosphoric acid potassium, react 3 hours after-filtration, the solid that obtains obtains butyl polyvinyl imidazol fluorophosphate (ionic liquid chain hop count is 19.7%), yield 84.9%, results of elemental analyses: C:51.61% through the oven dry of washing back; H:6.01%; N:20.81% (calculated value: C:51.91%; H:5.81%; N:20.93%).Its second-order transition temperature is 161 ℃.
Embodiment 9
Repeat embodiment 7, difference is to add 4.6 gram (0.025 mole) hexafluorophosphoric acid potassium, react 3 hours after-filtration, the solid that obtains obtains butyl polyvinyl imidazol fluorophosphate (ionic liquid chain hop count is 38.5%) through the oven dry of washing back, yield 86.5%, results of elemental analyses: C:45.69%; H:5.51%; N:16.30% (calculated value: C:45.07%; H:5.82%; N:16.44%), its second-order transition temperature is 163 ℃.
Embodiment 10
Repeat embodiment 5, difference is to add 13.8 gram (0.075 mole) hexafluorophosphoric acid potassium, reacts 0.5 hour after-filtration, and the solid that obtains obtains normal-butyl polyvinyl imidazol fluorophosphate, yield 89.5% through the oven dry of washing back.
Embodiment 11
Repeat embodiment 5, difference is to react 72 hours after-filtration, and the solid that obtains obtains normal-butyl polyvinyl imidazol fluorophosphate, yield 89.4% through the oven dry of washing back.
Embodiment 12
Repeat embodiment 2, resulting product is all put into Erlenmeyer flask, add 100 milliliters of ethanol make its dissolving after, under the stirring at room state, add 5.5 gram (0.05 mole) ammonium borofluorides, react 72 hours after-filtration, the filtrate oven dry obtains normal-butyl polyvinyl imidazol fluoroborate, yield 7.93%.
Embodiment 13
Repeat embodiment 3, resulting product is all put into Erlenmeyer flask, add 50 ml deionized water make its dissolving after, under 50 ℃ of whipped states, add 9.2 gram (0.05 mole) hexafluorophosphoric acid potassium, react 3 hours after-filtration, the solid that obtains obtains ethyl polyvinyl imidazol fluorophosphate (ionic liquid chain hop count is 88.0%), yield 90.2% through the oven dry of washing back.Results of elemental analyses: C:32.48%; H:4.04%; N:11.86% (calculated value: C:32.83%; H:4.21%; N:11.33%).INFRARED SPECTRUM: wave number (cm
-1): 3648.0,3417.5,3165.0,2997.7,1648.8,1573.9,1554.8,1501.8,1285.2,1161.6,1114.1,1088.7,835.4,662.0,557.6.
Embodiment 14
Repeat embodiment 4, resulting product is all put into Erlenmeyer flask, add 50 ml deionized water make its dissolving after, under 0 ℃ of whipped state, add 9.2 gram (0.05 mole) hexafluorophosphoric acid potassium, react 3 hours after-filtration, the solid that obtains obtains normal-butyl polyvinyl imidazol fluorophosphate (ionic liquid chain hop count is 9.8%), yield 90.8% through the oven dry of washing back.Results of elemental analyses: C:60.75%; H:5.16%; N:21.33% (calculated value: C:60.51%; H:5.28%; N:21.50%).INFRARED SPECTRUM: wave number (cm
-1): 3645.5,2926.5,2854.8,1502.0,1418.4,1232.2,1113.0,1086.2,832.0,739.4,662.1,557.4.
Claims (8)
1. one kind is gathered (N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material, it is characterized in that it has following general formula:
Wherein R is C
2-C
16Alkyl, X
-Be negative ion, the chain hop count that n, m represent to contain the chain hop count of ionogen respectively and do not contain ionogen, n: (n+m)=0.1: 1～1: 1, molecular weight Mn scope is (0.1-100) * 10
4G/mol.
2. poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material according to claim 1, it is characterized in that: described R is C
2-C
16Alkyl be meant straight or branched alkyl with 2-16 carbon atom; X
-For negative ion is meant X
-Be Cl
-, Br
-, or I
-Halogen anion or BF
4 -, PF
6 -, CF
3SO
3 -, (CF
3SO
2)
2N
-, (CF
3CF
2SO
2)
2N
-Or CF
3COO
-Negative ion.
3. poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material according to claim 1, it is characterized in that: described R is C
2-C
16Alkyl be meant straight chained alkyl with 2-16 carbon atom; X
-For negative ion is meant X
-Be BF
4 -Or PF
6 -
4. one kind prepares above-mentioned method of gathering (N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material, it is characterized in that it may further comprise the steps:
Step 1, polyvinyl imidazol is dissolved in the polar organic solvent;
Step 2, in the solution of step 1 gained, add the doubly C of mole proportioning of 0.1-2 according to the monomeric mole number of institute's dissolved polyvinyl
2-C
16Halogenated alkane;
Step 3, with vlil 3-72 hour of step 2 gained;
Step 4, stopped reaction steam reaction solvent, again product are dried to constant weight, obtain poly-(N-vinyl-N '-alkyl-imidazoles) the ionic liquid structured material of halogenation.
5. the preparation method of poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material according to claim 3, it is characterized in that: the polar organic solvent described in the step 1 is bigger alcohols of polarity or nitrile.
6. the preparation method of poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material according to claim 4, it is characterized in that: the mole number of the haloalkane that step 2 added by step 1 0.2～1.2 times of dissolved polyvinyl imidazol segment mole number, to obtain having poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material of different charge numbers
7. the preparation method of poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material according to claim 4, it is characterized in that: poly-(N-vinyl-N '-alkyl-imidazoles) the ionic liquid structured material of the described halogenation that obtains can be further carries out negative ion exchange with ammonium salt or sylvite or sodium salt etc. with required negative ion according to the method for chemical field routine in solvent, make the salt of poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material of required target negative ion.
8. the preparation method of poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material according to claim 7, it is characterized in that: the solvent that the negative ion clearing house is used is water, ethanol or water and ethanol mixed solvent, the salt consumption of target negative ion is 1.0～1.5 times of poly-(N-vinyl-N '-alkyl-imidazoles) ionic liquid structured material ionization segment mole number, the permutoid reaction time is 0.5-72 hour, and the temperature of permutoid reaction is 0～50 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100982087A CN1970582B (en) | 2006-12-04 | 2006-12-04 | Poly(N- ethenyl-N'-alkyl- imidazole) ion liquid structural material and its preparation method |
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